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Title: Compositional and orientational control in metal halide perovskites of reduced dimensionality

Abstract

Reduced-dimensional metal halide perovskites (RDPs) have attracted significant attention in recent years due to their promising light harvesting and emissive properties. We sought to increase the systematic understanding of how RDPs are formed. Here we report that layered intermediate complexes formed with the solvent provide a scaffold that facilitates the nucleation and growth of RDPs during annealing, as observed via in situ X-ray scattering. Transient absorption spectroscopy of RDP single crystals and films enables the identification of the distribution of quantum well thicknesses. These insights allow us to develop a kinetic model of RDP formation that accounts for the experimentally observed size distribution of wells. RDPs exhibit a thickness distribution (with sizes that extend above n = 5) determined largely by the stoichiometric proportion between the intercalating cation and solvent complexes. Here, the results indicate a means to control the distribution, composition and orientation of RDPs via the selection of the intercalating cation, the solvent and the deposition technique.

Authors:
 [1]; ORCiD logo [2]; ORCiD logo [1];  [3]; ORCiD logo [1]; ORCiD logo [1];  [3]; ORCiD logo [4]; ORCiD logo [1]
  1. Univ. of Toronto, Toronto, ON (Canada)
  2. SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford Univ., Stanford, CA (United States)
  3. King Abdullah Univ. of Science and Technology (KAUST), Thuwal (Saudi Arabia)
  4. SLAC National Accelerator Lab., Menlo Park, CA (United States)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1490652
Grant/Contract Number:  
AC02-76SF00515
Resource Type:
Accepted Manuscript
Journal Name:
Nature Materials
Additional Journal Information:
Journal Volume: 17; Journal Issue: 10; Journal ID: ISSN 1476-1122
Publisher:
Springer Nature - Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Quintero-Bermudez, Rafael, Gold-Parker, Aryeh, Proppe, Andrew H., Munir, Rahim, Yang, Zhenyu, Kelley, Shana O., Amassian, Aram, Toney, Michael F., and Sargent, Edward H. Compositional and orientational control in metal halide perovskites of reduced dimensionality. United States: N. p., 2018. Web. doi:10.1038/s41563-018-0154-x.
Quintero-Bermudez, Rafael, Gold-Parker, Aryeh, Proppe, Andrew H., Munir, Rahim, Yang, Zhenyu, Kelley, Shana O., Amassian, Aram, Toney, Michael F., & Sargent, Edward H. Compositional and orientational control in metal halide perovskites of reduced dimensionality. United States. doi:10.1038/s41563-018-0154-x.
Quintero-Bermudez, Rafael, Gold-Parker, Aryeh, Proppe, Andrew H., Munir, Rahim, Yang, Zhenyu, Kelley, Shana O., Amassian, Aram, Toney, Michael F., and Sargent, Edward H. Mon . "Compositional and orientational control in metal halide perovskites of reduced dimensionality". United States. doi:10.1038/s41563-018-0154-x. https://www.osti.gov/servlets/purl/1490652.
@article{osti_1490652,
title = {Compositional and orientational control in metal halide perovskites of reduced dimensionality},
author = {Quintero-Bermudez, Rafael and Gold-Parker, Aryeh and Proppe, Andrew H. and Munir, Rahim and Yang, Zhenyu and Kelley, Shana O. and Amassian, Aram and Toney, Michael F. and Sargent, Edward H.},
abstractNote = {Reduced-dimensional metal halide perovskites (RDPs) have attracted significant attention in recent years due to their promising light harvesting and emissive properties. We sought to increase the systematic understanding of how RDPs are formed. Here we report that layered intermediate complexes formed with the solvent provide a scaffold that facilitates the nucleation and growth of RDPs during annealing, as observed via in situ X-ray scattering. Transient absorption spectroscopy of RDP single crystals and films enables the identification of the distribution of quantum well thicknesses. These insights allow us to develop a kinetic model of RDP formation that accounts for the experimentally observed size distribution of wells. RDPs exhibit a thickness distribution (with sizes that extend above n = 5) determined largely by the stoichiometric proportion between the intercalating cation and solvent complexes. Here, the results indicate a means to control the distribution, composition and orientation of RDPs via the selection of the intercalating cation, the solvent and the deposition technique.},
doi = {10.1038/s41563-018-0154-x},
journal = {Nature Materials},
number = 10,
volume = 17,
place = {United States},
year = {2018},
month = {9}
}

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Works referenced in this record:

Efficient Visible Quasi-2D Perovskite Light-Emitting Diodes
journal, June 2016

  • Byun, Jinwoo; Cho, Himchan; Wolf, Christoph
  • Advanced Materials, Vol. 28, Issue 34
  • DOI: 10.1002/adma.201601369

Mercury CSD 2.0 – new features for the visualization and investigation of crystal structures
journal, March 2008

  • Macrae, Clare F.; Bruno, Ian J.; Chisholm, James A.
  • Journal of Applied Crystallography, Vol. 41, Issue 2
  • DOI: 10.1107/S0021889807067908

Single-Crystalline and Monodisperse LaF 3 Triangular Nanoplates from a Single-Source Precursor
journal, March 2005

  • Zhang, Ya-Wen; Sun, Xiao; Si, Rui
  • Journal of the American Chemical Society, Vol. 127, Issue 10
  • DOI: 10.1021/ja042801y

Nika : software for two-dimensional data reduction
journal, March 2012


Perovskite light-emitting diodes based on solution-processed self-organized multiple quantum wells
journal, September 2016


Light and oxygen induced degradation limits the operational stability of methylammonium lead triiodide perovskite solar cells
journal, January 2016

  • Bryant, Daniel; Aristidou, Nicholas; Pont, Sebastian
  • Energy & Environmental Science, Vol. 9, Issue 5
  • DOI: 10.1039/C6EE00409A

Synthesis and Growth Mechanism of Lead Sulfide Quantum Platelets in Lamellar Mesophase Templates
journal, August 2014

  • Morrison, Paul J.; Loomis, Richard A.; Buhro, William E.
  • Chemistry of Materials, Vol. 26, Issue 17
  • DOI: 10.1021/cm5020702

Signs of stability
journal, July 2015


PbS in polymers. From molecules to bulk solids
journal, December 1987

  • Wang, Y.; Suna, A.; Mahler, W.
  • The Journal of Chemical Physics, Vol. 87, Issue 12
  • DOI: 10.1063/1.453325

Hybrid Perovskite Thin-Film Photovoltaics: In Situ Diagnostics and Importance of the Precursor Solvate Phases
journal, November 2016

  • Munir, Rahim; Sheikh, Arif D.; Abdelsamie, Maged
  • Advanced Materials, Vol. 29, Issue 2
  • DOI: 10.1002/adma.201604113

One-Year stable perovskite solar cells by 2D/3D interface engineering
journal, June 2017

  • Grancini, G.; Roldán-Carmona, C.; Zimmermann, I.
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/ncomms15684

Two-Dimensional Semiconductor Nanocrystals: Properties, Templated Formation, and Magic-Size Nanocluster Intermediates
journal, December 2014

  • Wang, Fudong; Wang, Yuanyuan; Liu, Yi-Hsin
  • Accounts of Chemical Research, Vol. 48, Issue 1
  • DOI: 10.1021/ar500286j

Ligand-Stabilized Reduced-Dimensionality Perovskites
journal, February 2016

  • Quan, Li Na; Yuan, Mingjian; Comin, Riccardo
  • Journal of the American Chemical Society, Vol. 138, Issue 8
  • DOI: 10.1021/jacs.5b11740

Low trap-state density and long carrier diffusion in organolead trihalide perovskite single crystals
journal, January 2015


Excitonic Many-Body Interactions in Two-Dimensional Lead Iodide Perovskite Quantum Wells
journal, March 2015

  • Wu, Xiaoxi; Trinh, M. Tuan; Zhu, X. -Y.
  • The Journal of Physical Chemistry C, Vol. 119, Issue 26
  • DOI: 10.1021/acs.jpcc.5b00148

Determination of Exciton Diffusion Length by Transient Photoluminescence Quenching and Its Application to Quantum Dot Films
journal, April 2015

  • Lee, Elizabeth M. Y.; Tisdale, William A.
  • The Journal of Physical Chemistry C, Vol. 119, Issue 17
  • DOI: 10.1021/jp512634c

Polymer-templated nucleation and crystal growth of perovskite films for solar cells with efficiency greater than 21%
journal, September 2016


High-performance photovoltaic perovskite layers fabricated through intramolecular exchange
journal, May 2015


Perovskite energy funnels for efficient light-emitting diodes
journal, June 2016

  • Yuan, Mingjian; Quan, Li Na; Comin, Riccardo
  • Nature Nanotechnology, Vol. 11, Issue 10
  • DOI: 10.1038/nnano.2016.110

VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data
journal, October 2011


Hybrid perovskite solar cells: In situ investigation of solution-processed PbI 2 reveals metastable precursors and a pathway to producing porous thin films
journal, April 2017

  • Barrit, Dounya; Sheikh, Arif D.; Munir, Rahim
  • Journal of Materials Research, Vol. 32, Issue 10
  • DOI: 10.1557/jmr.2017.117

Ion Migration in Organometal Trihalide Perovskite and Its Impact on Photovoltaic Efficiency and Stability
journal, January 2016


Conducting tin halides with a layered organic-based perovskite structure
journal, June 1994

  • Mitzi, D. B.; Feild, C. A.; Harrison, W. T. A.
  • Nature, Vol. 369, Issue 6480, p. 467-469
  • DOI: 10.1038/369467a0

Long-Range Balanced Electron- and Hole-Transport Lengths in Organic-Inorganic CH3NH3PbI3
journal, October 2013


Size-Dependent Optical Properties of Colloidal PbS Quantum Dots
journal, September 2009

  • Moreels, Iwan; Lambert, Karel; Smeets, Dries
  • ACS Nano, Vol. 3, Issue 10
  • DOI: 10.1021/nn900863a

Structural absorption by barbule microstructures of super black bird of paradise feathers
journal, January 2018


Solvent engineering for high-performance inorganic–organic hybrid perovskite solar cells
journal, July 2014

  • Jeon, Nam Joong; Noh, Jun Hong; Kim, Young Chan
  • Nature Materials, Vol. 13, Issue 9, p. 897-903
  • DOI: 10.1038/nmat4014

Solvent engineering towards controlled grain growth in perovskite planar heterojunction solar cells
journal, January 2015

  • Rong, Yaoguang; Tang, Zhongjia; Zhao, Yufeng
  • Nanoscale, Vol. 7, Issue 24
  • DOI: 10.1039/C5NR02866C

Highly Efficient Perovskite-Quantum-Dot Light-Emitting Diodes by Surface Engineering
journal, August 2016


Ruddlesden–Popper Hybrid Lead Iodide Perovskite 2D Homologous Semiconductors
journal, April 2016

  • Stoumpos, Constantinos C.; Cao, Duyen H.; Clark, Daniel J.
  • Chemistry of Materials, Vol. 28, Issue 8, p. 2852-2867
  • DOI: 10.1021/acs.chemmater.6b00847

Synthesis, Optical Properties, and Self-Assembly of Ultrathin Hexagonal In2S3 Nanoplates
journal, July 2006

  • Park, Kang Hyun; Jang, Kwonho; Son, Seung Uk
  • Angewandte Chemie International Edition, Vol. 45, Issue 28
  • DOI: 10.1002/anie.200601031

Efficient and stable solution-processed planar perovskite solar cells via contact passivation
journal, February 2017


Experimental and theoretical optical properties of methylammonium lead halide perovskites
journal, January 2016

  • Leguy, Aurélien M. A.; Azarhoosh, Pooya; Alonso, M. Isabel
  • Nanoscale, Vol. 8, Issue 12
  • DOI: 10.1039/C5NR05435D

Organometal halide perovskite solar cells: degradation and stability
journal, January 2016

  • Berhe, Taame Abraha; Su, Wei-Nien; Chen, Ching-Hsiang
  • Energy & Environmental Science, Vol. 9, Issue 2
  • DOI: 10.1039/C5EE02733K

Observation of Internal Photoinduced Electron and Hole Separation in Hybrid Two-Dimentional Perovskite Films
journal, January 2017

  • Liu, Junxue; Leng, Jing; Wu, Kaifeng
  • Journal of the American Chemical Society, Vol. 139, Issue 4
  • DOI: 10.1021/jacs.6b12581

Characterization of an abnormal photoluminescence behavior upon crystal-phase transition of perovskite CH 3 NH 3 PbI 3
journal, January 2015

  • Kong, Weiguang; Ye, Zhenyu; Qi, Zhen
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 25
  • DOI: 10.1039/C5CP02605A

Perovskite photonic sources
journal, April 2016


High Charge Carrier Mobilities and Lifetimes in Organolead Trihalide Perovskites
journal, December 2013

  • Wehrenfennig, Christian; Eperon, Giles E.; Johnston, Michael B.
  • Advanced Materials, Vol. 26, Issue 10
  • DOI: 10.1002/adma.201305172

High-efficiency two-dimensional Ruddlesden–Popper perovskite solar cells
journal, July 2016

  • Tsai, Hsinhan; Nie, Wanyi; Blancon, Jean-Christophe
  • Nature, Vol. 536, Issue 7616
  • DOI: 10.1038/nature18306

Dynamic Optical Properties of CH 3 NH 3 PbI 3 Single Crystals As Revealed by One- and Two-Photon Excited Photoluminescence Measurements
journal, August 2015

  • Yamada, Yasuhiro; Yamada, Takumi; Phuong, Le Quang
  • Journal of the American Chemical Society, Vol. 137, Issue 33
  • DOI: 10.1021/jacs.5b04503

Lamellar Assembly of Cadmium Selenide Nanoclusters into Quantum Belts
journal, October 2011

  • Liu, Yi-Hsin; Wang, Fudong; Wang, Yuanyuan
  • Journal of the American Chemical Society, Vol. 133, Issue 42
  • DOI: 10.1021/ja206776g

Charge-Carrier Dynamics in 2D Hybrid Metal–Halide Perovskites
journal, October 2016


Structure of Organometal Halide Perovskite Films as Determined with Grazing-Incidence X-Ray Scattering Methods
journal, March 2017

  • Schlipf, Johannes; Müller-Buschbaum, Peter
  • Advanced Energy Materials, Vol. 7, Issue 16
  • DOI: 10.1002/aenm.201700131

2D Homologous Perovskites as Light-Absorbing Materials for Solar Cell Applications
journal, June 2015

  • Cao, Duyen H.; Stoumpos, Constantinos C.; Farha, Omar K.
  • Journal of the American Chemical Society, Vol. 137, Issue 24
  • DOI: 10.1021/jacs.5b03796

Observation of a hot-phonon bottleneck in lead-iodide perovskites
journal, October 2015


Low-threshold amplified spontaneous emission and lasing from colloidal nanocrystals of caesium lead halide perovskites
journal, August 2015

  • Yakunin, Sergii; Protesescu, Loredana; Krieg, Franziska
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms9056

An intrinsic growth instability in isotropic materials leads to quasi-two-dimensional nanoplatelets
journal, April 2017

  • Riedinger, Andreas; Ott, Florian D.; Mule, Aniket
  • Nature Materials, Vol. 16, Issue 7
  • DOI: 10.1038/nmat4889

    Works referencing / citing this record:

    High-resolution remote thermometry and thermography using luminescent low-dimensional tin-halide perovskites
    journal, July 2019


    Alcohol Vapor Post‐Annealing for Highly Efficient Sb 2 S 3 Planar Heterojunction Solar Cells
    journal, May 2019


    Heterogeneity at multiple length scales in halide perovskite semiconductors
    journal, July 2019

    • Tennyson, Elizabeth M.; Doherty, Tiarnan A. S.; Stranks, Samuel D.
    • Nature Reviews Materials, Vol. 4, Issue 9
    • DOI: 10.1038/s41578-019-0125-0

    Factors determining the vertical orientation of two-dimensional perovskites
    journal, January 2019

    • Arai, R.; Yoshizawa-Fujita, M.; Takeoka, Y.
    • CrystEngComm, Vol. 21, Issue 31
    • DOI: 10.1039/c9ce00631a

    Alcohol Vapor Post‐Annealing for Highly Efficient Sb 2 S 3 Planar Heterojunction Solar Cells
    journal, May 2019


    High-resolution remote thermometry and thermography using luminescent low-dimensional tin-halide perovskites
    journal, July 2019


    Heterogeneity at multiple length scales in halide perovskite semiconductors
    journal, July 2019

    • Tennyson, Elizabeth M.; Doherty, Tiarnan A. S.; Stranks, Samuel D.
    • Nature Reviews Materials, Vol. 4, Issue 9
    • DOI: 10.1038/s41578-019-0125-0

    Factors determining the vertical orientation of two-dimensional perovskites
    journal, January 2019

    • Arai, R.; Yoshizawa-Fujita, M.; Takeoka, Y.
    • CrystEngComm, Vol. 21, Issue 31
    • DOI: 10.1039/c9ce00631a

    Asymmetric alkyl diamine based Dion–Jacobson low-dimensional perovskite solar cells with efficiency exceeding 15%
    journal, January 2020

    • Zhao, Weidong; Dong, Qingshun; Zhang, Jiangwei
    • Journal of Materials Chemistry A, Vol. 8, Issue 19
    • DOI: 10.1039/d0ta02706e

    Impact of the Solvation State of Lead Iodide on Its Two‐Step Conversion to MAPbI 3 : An In Situ Investigation
    journal, January 2019

    • Barrit, Dounya; Cheng, Peirui; Tang, Ming‐Chun
    • Advanced Functional Materials, Vol. 29, Issue 47
    • DOI: 10.1002/adfm.201807544

    Compositional Control in 2D Perovskites with Alternating Cations in the Interlayer Space for Photovoltaics with Efficiency over 18%
    journal, September 2019


    Multiple‐Quantum‐Well Perovskites for High‐Performance Light‐Emitting Diodes
    journal, October 2019


    Optimization of Low‐Dimensional Components of Quasi‐2D Perovskite Films for Deep‐Blue Light‐Emitting Diodes
    journal, September 2019

    • Yuan, Shuai; Wang, Zhao‐Kui; Xiao, Lei‐Xin
    • Advanced Materials, Vol. 31, Issue 44
    • DOI: 10.1002/adma.201904319

    A 0D/3D Heterostructured All‐Inorganic Halide Perovskite Solar Cell with High Performance and Enhanced Phase Stability
    journal, October 2019


    Layered‐Perovskite Nanowires with Long‐Range Orientational Order for Ultrasensitive Photodetectors
    journal, January 2020


    Combining Efficiency and Stability in Mixed Tin–Lead Perovskite Solar Cells by Capping Grains with an Ultrathin 2D Layer
    journal, March 2020


    Controlling Spatial Crystallization Uniformity and Phase Orientation of Quasi‐2D Perovskite‐Based Light‐Emitting Diodes Using Lewis Bases
    journal, December 2019

    • Han, Yaeeun; Park, Sungbin; Wang, Jian
    • Advanced Materials Interfaces, Vol. 7, Issue 3
    • DOI: 10.1002/admi.201901860

    Spontaneous Formation of Nanocrystals in Amorphous Matrix: Alternative Pathway to Bright Emission in Quasi‐2D Perovskites
    journal, June 2019

    • Liu, Fangzhou; Chan, Christopher Chang Sing; Ma, Chao
    • Advanced Optical Materials, Vol. 7, Issue 19
    • DOI: 10.1002/adom.201900269

    Exploiting Two‐Step Processed Mixed 2D/3D Perovskites for Bright Green Light Emitting Diodes
    journal, May 2019

    • Yan, Jielin; Croes, Guillaume; Fakharuddin, Azhar
    • Advanced Optical Materials, Vol. 7, Issue 15
    • DOI: 10.1002/adom.201900465

    Reverse‐Graded 2D Ruddlesden–Popper Perovskites for Efficient Air‐Stable Solar Cells
    journal, April 2019

    • Wei, Yi; Chu, Huailong; Tian, Yuyang
    • Advanced Energy Materials, Vol. 9, Issue 21
    • DOI: 10.1002/aenm.201900612

    Anisotropically Electrochemical–Mechanical Evolution in Solid‐State Batteries and Interfacial Tailored Strategy
    journal, November 2019


    Anisotropically Electrochemical–Mechanical Evolution in Solid‐State Batteries and Interfacial Tailored Strategy
    journal, November 2019

    • Sun, Nan; Liu, Qingsong; Cao, Yi
    • Angewandte Chemie International Edition, Vol. 58, Issue 51
    • DOI: 10.1002/anie.201910993

    Charge Transport in Halide Perovskite Single Crystals: Experimental and Theoretical Perspectives
    journal, January 2019


    Two‐Dimensional Halide Perovskites in Solar Cells: 2D or not 2D?
    journal, March 2019

    • Ortiz‐Cervantes, Carmen; Carmona‐Monroy, Paulina; Solis‐Ibarra, Diego
    • ChemSusChem, Vol. 12, Issue 8
    • DOI: 10.1002/cssc.201802992

    Manipulating the Phase Distributions and Carrier Transfers in Hybrid Quasi‐Two‐Dimensional Perovskite Films
    journal, February 2019


    Interlayer Cross‐Linked 2D Perovskite Solar Cell with Uniform Phase Distribution and Increased Exciton Coupling
    journal, April 2020


    Below 200 °C Fabrication Strategy of Black‐Phase CsPbI 3 Film for Ambient‐Air‐Stable Solar Cells
    journal, January 2020


    Recent advances in controlling the crystallization of two-dimensional perovskites for optoelectronic device
    journal, May 2019


    Unveiling the operation mechanism of layered perovskite solar cells
    journal, March 2019


    Templated growth of oriented layered hybrid perovskites on 3D-like perovskites
    journal, January 2020


    Efficient blue light-emitting diodes based on quantum-confined bromide perovskite nanostructures
    journal, August 2019


    Dimensional tailoring of hybrid perovskites for photovoltaics
    journal, November 2018


    Multi-layered hybrid perovskites templated with carbazole derivatives: optical properties, enhanced moisture stability and solar cell characteristics
    journal, January 2018

    • Herckens, Roald; Van Gompel, Wouter T. M.; Song, Wenya
    • Journal of Materials Chemistry A, Vol. 6, Issue 45
    • DOI: 10.1039/c8ta08019d

    Simple fabrication of layered halide perovskite platelets and enhanced photoluminescence from mechanically exfoliated flakes
    journal, January 2019

    • Dhanabalan, Balaji; Castelli, Andrea; Palei, Milan
    • Nanoscale, Vol. 11, Issue 17
    • DOI: 10.1039/c9nr00638a

    Growth modes and quantum confinement in ultrathin vapour-deposited MAPbI 3 films
    journal, January 2019

    • Parrott, Elizabeth S.; Patel, Jay B.; Haghighirad, Amir-Abbas
    • Nanoscale, Vol. 11, Issue 30
    • DOI: 10.1039/c9nr04104d

    Trap passivation and efficiency improvement of perovskite solar cells by a guanidinium additive
    journal, January 2019

    • Yao, Jiaxu; Wang, Hui; Wang, Pang
    • Materials Chemistry Frontiers, Vol. 3, Issue 7
    • DOI: 10.1039/c9qm00112c

    Self-assembled propylammonium cations at grain boundaries and the film surface to improve the efficiency and stability of perovskite solar cells
    journal, January 2019

    • Fei, Chengbin; Zhou, Meng; Ogle, Jonathan
    • Journal of Materials Chemistry A, Vol. 7, Issue 41
    • DOI: 10.1039/c9ta01755k

    Structural and spectral dynamics of single-crystalline Ruddlesden-Popper phase halide perovskite blue light-emitting diodes
    journal, January 2020